DE1219154B - Process for the preparation of monoazo dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN WTTWt PATENT OFFICE Int. CL:

C09b

EDITORIAL

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German class: 22a-l

1219154
S72529IVc / 22a
February 14, 1961
June 16, 1966

The diazo compound from l-amino-2-cyano-4-nitro-6-halobenzene has already been used for the production of azo dyes that are sparingly soluble in water found (compare e.g. German patents 648 768 and 748 473, but the drawability of the known disperse dyes based on this on hydrophobic fibers leave something to be desired.

It has now been found that this disadvantage can be avoided by using the monoazo dyes formula

O ₂ N

N = N

in which χ chlorine or bromine, y hydrogen or the methyl or ethyl radical, R ₁ the methyl, ethyl or / 9-cyanoethyl radical and R ₂ a mono- or dihydroxyalkyl radical with 1, optionally etherified with low molecular weight alkyl groups or esterified with low molecular weight aliphatic carboxylic acids to 3 carbon atoms, by coupling one mole of the known diazo compound from 1-amino-2-cyano-4-nitro-6-halobenzene of the formula

O ₉ N-

NH,

(II)

with 1 mole of an azo component

(III)

produces, where the symbols in the formulas (II) and (III) have the meaning given above. "Low molecular weight" in this context means that the alkyl radicals and the carboxylic acid radicals preferably contain 1 to 4 carbon atoms and especially 1 or 2 carbon atoms. The dyes of the formula (I) have particularly good properties if χ chlorine or bromine, y a hydrogen atom or the methyl radical, R ₁ the methyl or ethyl radical and R ₂ an optionally etherified or esterified monohydroxyalkyl radical with 1 to 3 carbon atoms means.

Process for the production of
Monoazo dyes

Applicant:

Sandoz A. G., Basel (Switzerland)

Representative:

Dr. W. Schalk, Dipl.-Ing. P. Wirth,

Dipl.-Ing. G. E. M. Dannenberg

and Dr. V. Schmied-Kowarzik, patent attorneys,

Frankfurt / M., Große Eschenheimer Str. 39.

Named as inventor:

Dr. Ernest Merian, Bottmingen; ^:

Dr. Curt Müller, Basel (Switzerland) "" '

Claimed priority:
Switzerland February 16, 1960 ^(1721):
of January 27, 1961 (1002, 1003)

The coupling of the diazo compounds with the azo components is carried out in a customary manner, preferably carried out in acidic, optionally buffered, medium.

The new azo dyes, which are sparingly soluble in water, are suitable for dyeing, padding and printing hydrophobic fibers, threads and fiber materials of all kinds, in particular made of cellulose ester fibers (e.g. acetate rayon or triacetate rayon) or from linear aromatic polyesters, especially from terephthalic acid and glycols, especially ethylene glycol or p-xylylene glycol.

The drawing and build-up to 2V ₂ - and 3-Acetatkunstseide is excellent. The red to violet dyeings obtained in this way are distinguished by good fastness to light, water, washing, smoke gas, sublimation and pleating and are readily etchable. Viscose, cotton and wool in blended fabrics are well reserved.

Compared to colorations with the closest comparable dyes of German patent specification 648 768 and U.S. Pat. No. 2,173,417, those with the new dyes on acetate silk have a better one Smoke gas resistance.

The dyeings on polyester fibers have almost the same shade as stains on 2V ₂ - and 3-Acetatkunstseide and also good light, washing,

609 579/367

Fastness to sublimation and thermal fixation. Also on this one Fibers are excellent in drawing and building power. While so far no lightfast violet azo dyes are known to have good drawing and build-up properties on acetate rayon, especially the new blue-violet dyes this property to an excellent degree, so that they can be used, for example, together with yellow and possibly blue dyes for the production of cheap light, washing, sweat, Flue gas, sublimation and pleat-proof navy blue and black colorations are suitable.

In the following examples, parts are parts by weight and percentages are percentages by weight. The .. temperatures are given in degrees Celsius.

example 1

6.9 parts of sodium nitrite are added to 110 parts of 96% strength sulfuric acid at 60 ° to 70 °. The thus obtained Nitrosylsulfuric acid is cooled to 20 ° and 100 parts of glacial acetic acid are added, then, also at 20 °, 24.2 parts l-Amino ^ -cyan-i-nitro-ö-bromobenzene and finally 100 parts of glacial acetic acid are added dropwise. The resulting solution is stirred at 20 ° for 2 hours. You let them obtained diazo solution at 0 ° to a mixture of 22.1 parts of l- (N-ethyl-N-acetoxyethyl) -amino-3-methylbenzene, 200 parts of glacial acetic acid and 200 parts of ice flow. The temperature is thereby increased by adding Ice kept at 0 °. The purple dye precipitates immediately. It is filtered off, washed with water and dried. It dissolves in concentrated sulfuric acid with a red-brown color and melts again at 134 ° Recrystallize from a mixture of acetone and ethanol. In aqueous dispersion it can be used for Dyeing of acetate rayon and polyester fibers in reddish purple tones are used. ,

The corresponding dye from the diazo compound of l-amino-2-cyano-4-nitro-6-chlorobenzene melts at 113 °.

Example 2

If, in Example 1, the diazo component is replaced by diazotized l-amino ^ -cyan ^ nitro-ö -chlorobenzene and the coupling component

l- (N-ethyl-N-hydroxyethyl) -amino-3-methylbenzene, a purple powder is obtained, which is concentrated in Sulfuric acid dissolves with a red color, and, converted from alcohol, has a melting point of 176 °. The dyeings on acetate rayon and polyester

ao fibers have a brilliant purple shade.

The one from the diazo component of l-amino-2-cyano-4-nitro-6-bromobenzene The corresponding dye obtained melts after recrystallization from alcohol and acetone at 178 to 180 °.

The following table lists further dyes which, according to the information in Example 1 be produced. They skid by their melting point and the tone of the dyeings on acetate rayon.

at
game χ y. R ₁ R ₂ Melting point
in ° C Hue on
Acetate silk 3
4th
5
6th QQQQ -CH ₃
- Η
- Η
-CH ₃ -CH ₂ -CH ₂ -CN
-CH ₂ -CH ₂ -CN
-CH ₂ -CH ₂ -CN
-CH ₂ -CH ₂ -CN -CH ₂ -CH ₂ -OH
-CH ₂ -CH ₂ -OH
- CH ₂ - CH ₂ - O - CO - CH ₃
-CH ₂ -CH ₂ -O-CO-CH ₃ 195 to 196
182
179
151 Bluish red
Bluish red
Bluish red
Red-violet

Example 7

One from 19.7 parts of l-amino ^ -cyan ^ -nitro-ö -chlorobenzene Diazo solution produced is treated with a solution of 16.5 parts of l- (N-ethyl-N-hydroxyethyl) aminobenzene combined in glacial acetic acid with the addition of ice. The coupling is ended by adding sodium acetate. The dye obtained, a dark powder, dissolves in concentrated sulfuric acid with a light brown color and in acetone with purple color. Recrystallized from acetone and alcohol, it melts at 191 °. He dyes acetate artificial silk and polyester fibers in reddish-violet shades from an aqueous dispersion.

Example 8

One from 19.7 parts of l-amino ^ -cyan ^ -nitro-ö -chlorobenzene Diazo solution produced is treated with a solution of 20.7 parts of 1- (N-ethyl-N-acetoxyethyl) aminobenzene combined in glacial acetic acid with the addition of ice. The coupling is ended by adding sodium acetate. The dye obtained dissolves in concentrated sulfuric acid with a red-brown color and in acetone with a red-violet color. After recrystallization from a mixture of alcohol and dimethylformamide it melts at 128 °. Acetate rayon and polyester fibers are made from an aqueous dispersion reddish purple tones.

The corresponding obtained with l- (N-methyl-N-acetoxyethyl) aminobenzene as the coupling component After recrystallization, the dye melts at 153 °. It is also an excellent dye.

Example 9

One from 19.7 parts of 1-amino-2-cyano'4-nitro-6-chlorobenzene Diazo solution prepared is mixed with a solution of 20.9 parts of N-ethyl-N- ^ y-dihydroxypropyl-m-toluidine combined in 200 parts of 15% igar hydrochloric acid with the addition of ice. The coupling is completed Addition of sodium acetate. The dye obtained dissolves in concentrated sulfuric acid with red-brown Color and in acetone with purple color. After recrystallization from alcohol, it melts at 157 °. Acetate artificial silk and polyester fibers are dyed in violet shades from an aqueous dispersion

Claims (1)

Claim: Process for the preparation of monoazo dyes, characterized in that one mole of the diazo compound from an amine of the formula CN O ₂ N NH ₂ with 1 mole of an azo component of the formula to a dye of the formula CN O ₂ N (III) N = N couples, where in the formers χ chlorine or bromine, y hydrogen or the methyl or ethyl radical, R ₁ the methyl, ethyl or /? - cyanoethyl radical and R ₂ a mono- or is a dihydroxyalkyl radical having 1 to 3 carbon atoms. Considered publications: German Patent No. 648 768;
U.S. Patent No. 2173,417. When the application was announced, a coloring table with explanations was laid out. 609 579/367 6.66 © Bundesdruckerei Berlin